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United States Patent |
5,081,133
|
Schubert
,   et al.
|
January 14, 1992
|
2-Anilinocyanopyridines having fungicidal properties
Abstract
2-Anilinocyanopyridines of the formula
##STR1##
where X is NO.sub.2, CN, halogen, SO.sub.2 -alkyl, alkyl, cycloalkyl,
haloalkyl, alkoxy, or phenoxy or phenylthio which is unsubstituted or
substituted in the phenyl,
m is an integer from 1 to 3,
R.sup.1 is hydrogen, halogen, alkoxy, haloalkyl, haloalkoxy, or phenoxy or
phenylthio which is unsubstituted or substituted in the phenyl,
R.sup.2 and R.sup.3 are hydrogen, NO.sub.2, halogen, CN, alkyl, SO.sub.2
-alkyl, haloalkyl, SO.sub.2 NR.sup.5 R.sup.6, haloalkoxy, COOR.sup.5 or
CONR.sup.5 R.sup.6,
R.sup.4 is hydrogen, COOR.sup.7, CONR.sup.5 R.sup.6, CHO, COR.sup.7,
SO.sub.2 R.sup.7, C.sub.3 -C.sub.6 -alkenyl or C.sub.3 -C.sub.6 -alkynyl,
and salts of these 2-anilinocyanopyridines of the formula I in which
R.sup.4 is hydrogen with plant-tolerated cations, and fungicides
containing these compounds.
Inventors:
|
Schubert; Juergen (Mannheim, DE);
Wild; Jochen (Deidesheim, DE);
Harreus; Albrecht (Ludwigshafen, DE);
Kuekenhoehner; Thomas (Frankenthal, DE);
Sauter; Hubert (Mannheim, DE);
Ammermann; Eberhard (Ludwigshafen, DE);
Lorenz; Gisela (Neustadt, DE)
|
Assignee:
|
BASF Aktiengesellschaft (Ludwigshafen, DE)
|
Appl. No.:
|
470309 |
Filed:
|
January 25, 1990 |
Foreign Application Priority Data
Current U.S. Class: |
514/344; 546/286; 546/287; 546/289 |
Intern'l Class: |
C07D 213/74; C07D 213/85; A01N 043/40 |
Field of Search: |
546/286,287,289
71/94
514/344
|
References Cited
U.S. Patent Documents
4331670 | May., 1982 | Nishiyama et al. | 514/349.
|
4395555 | Jul., 1983 | Acker et al. | 546/289.
|
Foreign Patent Documents |
3528459 | Aug., 1985 | DE | 546/287.
|
Other References
March, Advanced Organic Chemistry, Second Edition, pp. 460-466, McGraw-Hill
Pub. QD 251 M2 1977, C.5.
Jerry March, Advanced Organic Chemistry Reactions, Mechanisms, and
Structure, Third Edition, pp. 598-600, 1086-1087, 1089-1090, 1985, New
York, N.Y.
Alan R. Katritzky, Handbook of Heterocyclic Chemistry, pp. 145-146, 1985,
New York, N.Y.
Jerry March, Advanced Organic Chemistry Reactions, Mechanisms, and
Structure, SEcond Edition, pp. 658-659, 1977, New York, N.Y.
CRC Handbook of Chemistry and Physics, 64th Edition, C-488-9, C-90-160,
1983-1984, Boca Raton, Fla.
|
Primary Examiner: Rotman; Alan L.
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier & Neustadt
Claims
We claim:
1. A 2-anilinocyanopyridine of the formula I
##STR21##
where X is H, NO.sub.2, CN, halogen, SO.sub.2 --C.sub.1 -C.sub.4 -alkyl,
C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.4
-haloalkyl, C.sub.1 -C.sub.4 -alkoxy, phenoxy, phenoxy substituted from
one to three times with halogen or from one to two times with nitro or
methyl, phenylthio or phenylthio substituted from one to three times with
halogen or from one to two times with nitro or methyl,
m is an integer from 1 to 3, with the individual radicals being identical
or different when m is greater than 1,
R.sup.1 is hydrogen, halogen, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4
-haloalkyl, C.sub.1 -C.sub.4 -haloalkoxy, phenoxy, phenoxy substituted
from one to three times with halogen or from one to two times with nitro
or methyl, phenylthio or phenylthio substituted from one to three times
with halogen or from one to two times with nitro or methyl,
R.sup.2 and R.sup.3 are, independently of one another, hydrogen, NO.sub.2,
halogen, CN, C.sub.1 -C.sub.6 -alkyl, SO.sub.2 --C.sub.1 -C.sub.4 -alkyl,
C.sub.1 -C.sub.6 -haloalkyl, SO.sub.2 NR.sup.5 R.sup.6, C.sub.1 -C.sub.4
-haloalkoxy, COOR.sup.5 or CONR.sup.5 R.sup.6,
R.sup.4 is hydrogen, COOR.sup.7, CONR.sup.5 R.sup.6, CHO, COR.sup.7,
SO.sub.2 R.sup.7, C.sub.3 -C.sub.6 -alkenyl or C3-C6-alkynyl,
R.sup.5 and R.sup.6 are, independently of one another, hydrogen or C.sub.1
-C.sub.4 -alkyl,
R.sup.7 is C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, benzyl,
phenyl, 2-tolyl, 3-tolyl, 4-tolyl, halophenyl, nitrophenyl, 1-naphthyl or
2-naphthyl,
or a salt of said 2-anilinocyanopyridine of the formula I in which R.sup.4
is hydrogen with a plant-tolerated cation.
2. A compound of the formula I as set forth in claim 1, where X.sub.m is
4-isopropyl, 3-cyano, 5-cyano, 6-ethoxy, R.sup.1 is chlorine, R.sup.2 is
trifluoromethyl, R.sup.3 is nitro and R.sup.4 is hydrogen.
3. A compound of the formula I as set forth in claim 1, where X.sub.m is
3-chloro, 5-cyano, R.sup.1 is hydrogen, R.sup.2 is trifluoromethyl,
R.sup.3 is hydrogen and R.sup.4 is benzenesulfonyl.
4. The A 2-anilinocyanopyridine of claim 1, wherein m is an integer from 1
to 2.
5. A fungicidal composition comprising a fungicidally effective amount of a
compound of the formula I
##STR22##
where X is H, NO.sub.2, CN, halogen, SO.sub.2 --C.sub.1 -C.sub.4 -alkyl,
C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.4
-haloalkyl, C.sub.1 -C.sub.4 -alkoxy, phenoxy, phenoxy substituted from
one to three times with halogen or from one to two times with nitro or
methyl, phenylthio or phenylthio substituted from one to three times with
halogen or from one to two times with nitro or methyl,
m is an integer from 1 to 3, with the individual radicals being identical
or different when m is greater than 1,
R.sup.1 is hydrogen, halogen, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4
-haloalkyl, C.sub.1 -C.sub.4 -haloalkoxy, phenoxy, phenoxy substituted
from one to three times with halogen or from one to two times with nitro
or methyl, phenylthio or phenylthio substituted from one to three times
with halogen or from one to two times with nitro or methyl,
R.sup.2 and R.sup.3 are, independently of one another, hydrogen, NO.sub.2,
halogen, CN, C.sub.1 -C.sub.6 -alkyl, SO.sub.2 --C.sub.1 -C.sub.4 -alkyl,
C.sub.1 -C.sub.6 -haloalkyl, SO.sub.2 NR.sup.5 R.sup.6, C.sub.1 -C.sub.4
-haloalkoxy, COOR.sup.5 or CONR.sup.5 R.sup.6,
R.sup.4 is hydrogen, COOR.sup.7, CONR.sup.5 R.sup.6, CHO, COR.sup.7,
SO.sub.2 R.sup.7, C.sub.3 -C.sub.6 -alkenyl or C.sub.3 -C.sub.6 -alkynyl,
R.sup.5 and R.sup.6 are, independently of one another, hydrogen or C.sub.1
-C.sub.4 -alkyl,
R.sup.7 is C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, benzyl,
phenyl, 2-tolyl, 3-tolyl, 4-tolyl, halophenyl, nitrophenyl, 1-naphthyl or
2-naphthyl,
or a salt of said 2-anilinocyanopyridine of the formula I in which R.sup.4
is hydrogen with a plant-tolerated cation in admixture with a suitable
inert carrier.
6. The fungicidal composition of claim 5, wherein m is an integer from 1 to
2.
7. A method for combating fungi, comprising applying a fungicidally
effective amount of a compound of the formula
##STR23##
where X is H, NO.sub.2, CN, halogen, SO.sub.2 --C.sub.1 -C.sub.4 -alkyl,
C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.4
-haloalkyl, C.sub.1 -C.sub.4 -alkoxy, phenoxy, phenoxy substituted from
one to three times with halogen or from one to two times with nitro or
methyl, phenylthio or phenylthio substituted from one to three times with
halogen or from one to two times with nitro or methyl,
m is an integer from 1 to 3, with the individual radicals being identical
or different when m is greater than 1,
R.sup.1 is hydrogen, halogen, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4
-haloalkyl, C.sub.1 -C.sub.4 -haloalkoxy, phenoxy, phenoxy substituted
from one to three times with halogen or from one to two times with nitro
or methyl, phenylthio or phenylthio substituted from one to three times
with halogen or from one to two times with nitro or methyl,
R.sup.2 and R.sup.3 are, independently of one another, hydrogen, NO.sub.2,
halogen, CN, C.sub.1 -C.sub.6 -alkyl, SO.sub.2 --C.sub.1 -C.sub.4 -alkyl,
C.sub.1 -C.sub.6 -haloalkyl, SO.sub.2 NR.sup.5 R.sup.6, C.sub.1 -C.sub.4
-haloalkoxy, COOR.sup.5 or CONR.sup.5 R.sup.6,
R.sup.4 is hydrogen, COOR.sup.7, CONR.sup.5 R.sup.6, CHO, COR.sup.7,
SO.sub.2 R.sup.7, C.sub.3 -C.sub.6 -alkenyl or C.sub.3 -C.sub.6 -alkynyl,
R.sup.5 and R.sup.6 are, independently of one another, hydrogen or C.sub.1
-C.sub.4 -alkyl,
R.sup.7 is C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, benzyl,
phenyl, 2-tolyl, 3-tolyl, 4-tolyl, halophenyl, nitrophenyl, 1-naphthyl or
2-naphthyl,
or a salt of said 2-anilinocyanopyridine of the formula I in which R.sup.4
is hydrogen with a plant-tolerated cation to a locus subject to fungal
infection.
8. The method for combating fungi of claim 7, wherein m is an integer from
1 to 2.
Description
The present invention relates to novel, valuable 2-anilinocyanopyridines,
processes for the preparation thereof, fungicidal agents containing these
compounds and the use thereof as fungicides.
It has been disclosed that 2-anilinopyridines, for example
2-(2,4-dinitro-6-trifluoromethylanilino)-5-trifluoromethylpyridine (EP-A
31 257) have a good fungicidal action. However, the action is not always
satisfactory at low application rates and use concentrations.
We have now found, surprisingly, that 2-anilinocyanopyridines of the
formula I
##STR2##
where X is NO.sub.2, CN, halogen, SO.sub.2 --C.sub.1 -C.sub.4 -alkyl,
C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.4
-haloalkyl, C.sub.1 -C.sub.4 -alkoxy, or phenoxy or phenylthio which can
be substituted in the phenyl,
m is an integer from 1 to 3, with the individual radicals being identical
or different when m is greater than 1,
R.sup.1 is hydrogen, halogen, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4
-haloalkyl, C.sub.1 -C.sub.4 -haloalkoxy, or phenoxy or phenylthio which
can be substituted in the phenyl,
R.sup.2 and R.sup.3 are, independently of one another, hydrogen, NO.sub.2,
halogen, CN, C.sub.1 -C.sub.6 -alkyl, SO.sub.2 --C.sub.1 -C.sub.4 -alkyl,
C.sub.1 -C.sub.6 -haloalkyl, SO.sub.2 NR.sup.5 R.sup.6, C.sub.1 -C.sub.4
-haloalkoxy, COOR.sup.5 or CONR.sup.5 R.sup.6,
R.sup.4 is hydrogen, COOR.sup.7, CONR.sup.5 R.sup.6, CHO, COR.sup.7,
SO.sub.2 R.sup.7, C.sub.3 -C.sub.6 -alkenyl or C.sub.3 -C.sub.6 -alkynyl,
R.sup.5 and R.sup.6 are, independently of one another, hydrogen or C.sub.1
-C.sub.4 -alkyl,
R.sup.7 is C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -haloalkyl, benzyl, or
aryl which can be substituted,
and salts of the 2-anilinocyanopyridines of the formula I in which R.sup.4
is hydrogen with cations which are tolerated by plants, have a very good
fungicidal action and are excellently tolerated by plants.
The term alkyl means, on its own or as part of another substituent such as
haloalkyl, alkoxy or haloalkoxy, depending on the number of carbon atoms
indicated, the following straight-chain or branched groups: methyl, ethyl,
n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl
and n-hexyl. The prefix halo in the name of a substituent means, here and
hereinafter, that this substituent can be mono- to perhalogenated. Halogen
represents F, Cl, Br or I. Haloalkyl is thus a mono- to perhalogenated
alkyl such as CH.sub.2 Cl, CHCl.sub.2, CCl.sub.3, CH.sub.2 F, CHF.sub.2,
CF.sub.3, CH.sub.2 Br, CHBrCl, CF.sub.2 Cl, C.sub.2 Cl.sub.5, C.sub.2
F.sub.5, CF.sub.2 --CHF.sub.2, CH.sub.2 CH.sub.2 Cl, CH.sub.2 CH.sub.2 Br,
C.sub.3 F.sub.7 or C.sub.4 F.sub.9.
Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, it being
possible for the rings to be substituted by one or two methyls, such as
1-methylcyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl,
1-methylcyclopentyl or 1-methylcyclohexyl.
Examples of alkenyl are allyl, 3-butenyl, 4-butenyl, trans-2-butenyl and
cis-2-butenyl.
Examples of alkynyl are propargyl, 3-butynyl, 4-butynyl and 5-pentynyl.
Examples of aryl which can be substituted are phenyl, 2-, 3- and 4-tolyl,
halophenyl, 4-bromophenyl, 4-chlorophenyl, 4-fluorophenyl, nitrophenyl,
2-nitrophenyl, 4-nitrophenyl, and 1- and 2-naphthyl.
The meaning of phenoxy or phenylthio which can be substituted is that the
aromatic ring is unsubstituted or can be halogenated one to three times,
such as 2-Cl, 2-F, 3-Cl, 4-Cl, 4-Br, 2,3-Cl.sub.2, 2,4-Cl.sub.2,
2,5-Cl.sub.2, 2,6-Cl.sub.2, 3,5-Cl.sub.2, 2,4,6-Cl.sub.3 or
3,4,5-Cl.sub.3, or can have one or two substituents such as nitro or
methyl, for example 2-NO.sub.2, 4-NO.sub.2, 2-CH.sub.3, 4-CH.sub.3,
2,6-(CH.sub.3).sub.2 or 3,5-(CH.sub.3).sub.2.
Examples of suitable cations for the salts are the following: Na.sup.+,
K.sup.+, Mg.sup.2+, Fe.sup.3+ and NH.sub.4.sup.+, ammonium cations which
are alkylated, hydroxyalkylated and/or arylated one or more times, such as
diisopropylammonium, tetramethylammonium, tetrabutylammonium,
trimethylbenzylammonium, N,N-dimethylanilinium or
trimethyl(2-hydroxyethyl)ammonium, where the alkyl has 1 to 4 carbon atoms
and the aryl is phenyl or benzyl.
The compounds of the formula I as claimed in claim 1, in which R.sup.4 is
hydrogen, are prepared, for example, by reacting a cyanopyridine of the
formula II
##STR3##
where X and M have the meanings specified in claim 1, with compounds of
the formula III
##STR4##
where R.sup.1, R.sup.2 and R.sup.3 have the meanings specified in claim 1,
as the substance or in a solvent or diluent, in the presence or absence of
an organic or inorganic base, at from -20.degree. to 200.degree. C., where
Y and Z are NH.sub.2 or halogen and Y and Z are different from one
another.
In both cases the reaction takes place with elimination of hydrogen halide.
It is therefore advantageous in both cases to use acid-binding agents or
bases.
Bases or acid-binding agents which can be used are organic or inorganic
compounds such as alkali metal and alkaline earth metal hydroxides (LiOH,
NaOH, KOH, Ca(OH).sub.2), oxides (Na.sub.2 O, Li.sub.2 O, CaO, MgO),
hydrides (LiH, NaH, KH, CaH.sub.2), amides (LiNH.sub.2 NaNH.sub.2,
KNH.sub.2), carbonates (Li.sub.2 CO.sub.3, Na.sub.2 CO.sub.3, CaCO.sub.3),
bicarbonates (NaHCO.sub.3), alkyls (butylLi, CH.sub.3 Li, CH.sub.3 MgCl),
C.sub.1 -C.sub.5 -alcoholates (NaOCH.sub.3, NaOC.sub.2 H.sub.5, KOC.sub.2
H.sub.5, KO-tert-butyl, Mg(OCH.sub.3).sub.2) or amines, especially the
tertiary amines (e.g. trimethylamine, triethylamine,
diisopropylethylamine, N-methylpiperidine), pyridine, substituted
pyridines (collidine, lutidines, 4-dimethylaminopyridine) or bicyclic
amines.
The reactions can be carried out in the presence of solvents or diluents
which are inert under the reaction conditions.
Suitable examples are aliphatic and aromatic hydrocarbons such as toluene,
xylenes, cyclohexane and petroleum ether; halohydrocarbons such as
chlorobenzene, methylene chloride and chloroform; ethers and ether-like
compounds such as dialkyl ethers (diethyl ether, diisopropyl ether,
tert-butyl methyl ether etc.), anisole, dioxane and tetrahydrofuran;
nitriles such as acetonitrile, propionitrile, N,N-dialkylated amides such
as dimethylformamide; dimethyl sulfoxide; ketones such as acetone, diethyl
ketone and methyl ethyl ketone, alcohols such as methanol, ethanol, n- and
iso-propanol, butanols, especially tert-butanol, and mixtures of such
solvents.
The reaction temperature can be varied within wide limits. Depending on the
nature of the substituents X, R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6,
R.sup.7 and the number m thereof, the temperatures are from -20.degree. C.
to 200.degree. C. or the boiling point of the solvent or solvent mixture.
It may also be advantageous in some cases to carry out the reaction under
an atmosphere of protective gas and/or in anhydrous solvents. Suitable
protective gases are inert gases such as helium, argon etc., preferably
nitrogen.
The starting compounds are commercially available or are known or can be
prepared easily by conventional methods. The haloaromatic compounds (or
phenols which can be easily converted into these) and anilines which are
employed are commercially available.
Reference may be made to the following for 2-amino- and
2-halo-cyanopyridines: DE-A 31 03 065 and DE-A 35 28 459.
2-Amino- and 2-halo-cyanopyridines which have not yet been described can be
prepared from substituted 2-hydroxypyridines or substituted
pyridinecarboxylic acids by conventional methods of chemical synthesis.
For example
##STR5##
The compounds of the formula I, as claimed in claim 1 with the proviso that
R.sup.4 is not hydrogen, are prepared, for example, by reacting a
cyanopyridine of the formula I in which R.sup.4 is hydrogen, and X, m,
R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6 and R.sup.7 have the meanings
specified in claim 1, with an alkylating, acylating or sulfonylating agent
of the formula IV
LR.sup.4 IV
where R.sup.4 has the meaning specified in claim 1 apart from hydrogen, and
L is a leaving group which can be displaced nucleophilically, as the
substance or in the presence of a solvent or diluent and in the presence
or absence of an organic or inorganic base at from -20.degree. C. to
150.degree. C.
Suitable and preferred groups which can be displaced nucleophilically are
halogens such as F, Cl, Br and I, sulfonates (methanesulfonate,
benzenesulfonate etc.), alcoholates (ethylate, benzylate etc.) and
carboxylates (acetate etc.).
The bases which can be used are the same compounds used for the preparation
of compounds of the formula I (R.sup.4 =H) from compounds of the formulae
II and III.
The reaction temperatures are generally from -20.degree. C. to 150.degree.
C. or at the boiling point of the solvent or solvent mixture.
It is possible for one or more solvents or diluents which are inert under
the reaction conditions to be present during the reaction. Suitable
examples are aliphatic and aromatic hydrocarbons such as toluene, xylenes,
cyclohexane and petroleum ethers; halohydrocarbons such as chlorobenzene,
methylene chloride, ethylene chloride, chloroform and tetrachloroethylene;
ethers and ether-like compounds such as dialkyl ethers (diethyl ether,
diisopropyl ether, tert-butyl methyl ether etc.), anisole, dioxane and
tetrahydrofuran; nitriles such as acetonitrile and propionitrile;
N,N-dialkylated amides such as dimethylformamide; dimethyl sulfoxide;
ketones such as acetone, diethyl ketone and methyl ethyl ketone, and
mixtures of such solvents.
The novel compounds are isolated by conventional methods. The resulting
products can be purified by recrystallization, extraction or
chromatography. The examples which follow are intended to illustrate the
preparation:
EXAMPLE 1
A solution of 56.6 g (0.51 mol) of potassium tert-butylate in 500 ml of
tert-butanol is added dropwise within 1 h to a vigorously stirred
suspension of 57.5 g (0.25 mol) of
2-amino-3,5-dicyano-6-ethoxy-4-isopropylpyridine and 83.8 g (0.275 mol) of
1,3-dichloro-2,6-dinitro-4-trifluoromethylbenzene in 600 ml of 1:1
tetrahydrofuran/tert-butanol at 0.degree.-5.degree. C. After 1 h at
0.degree. C., the mixture is warmed to room temperature (20.degree. C.)
within 2 h, and then acidified with glacial acetic acid (pH 4), diluted
with 2 l of water and extracted 3 times with 50 ml of diethyl ether each
time. The combined ether extracts are washed with saturated brine, dried
over MgSO.sub.4 and concentrated, and the residue is stirred with ethanol;
72 g (58% of theory) of compound 1.239 are obtained as yellow crystals of
melting point 165.degree.- 167.degree. C.
EXAMPLE 2
0.24 g (0.01 mol) of sodium hydride is added a little at a time to a
solution of 3.4 g (0.01 mol) of
3-chloro-5-cyano-2-(2-nitro-4-trifluoromethylanilino)pyridine (compound
3.58) in 25 ml of tetrahydrofuran. After 15 min, 3.5 g (0.02 mol) of
benzenesulfonyl chloride are added dropwise at room temperature. After 48
h at 60.degree. C., 150 ml of water are added and the mixture is extracted
3 times with 100 ml of ether each time. The combined ether extracts are
washed with saturated brine, dried over MgSO.sub.4 and concentrated. The
residue is chromatographed (silica gel, 9:1 cyclohexane/ethyl acetate).
1.5 g (31% of theory) of compound 5.12 are obtained as yellow crystals of
melting point 147.degree.-158.degree. C.
The compounds described in the following Tables can be prepared using these
methods.
TABLE 1
__________________________________________________________________________
3-Cyanopyridine derivatives
##STR6##
No.
X.sub.m R.sup.1
R.sup.2
R.sup.3
m.p. (.degree.C.)
__________________________________________________________________________
1.1
H Cl CF.sub.3
NO.sub.2
157-158
1.2
H Cl CN NO.sub.2
1.3
H Cl COOC.sub.2 H.sub.5
NO.sub.2
1.4
H Cl CONH.sub.2
NO.sub.2
1.5
H Cl COOH NO.sub.2
1.6
H F CF.sub.3
NO.sub.2
1.7
H OCH.sub.3
CF.sub.3
NO.sub.2
1.8
H H CF.sub.3
NO.sub.2
1.9
H H CN NO.sub.2
1.10
H H Cl NO.sub.2
1.11
H Cl Cl NO.sub.2
1.12
H H SO.sub.2 CH.sub.3
NO.sub.2
1.13
H H COOCH.sub.3
NO.sub.2
1.14
H H CH.sub.3
NO.sub.2
1.15
H H NO.sub.2
CF.sub.3
112-115
1.16
H H NO.sub.2
Cl
1.17
H H NO.sub. 2
##STR7##
1.18
H Cl Cl Cl
1.19
5-Cl Cl CF.sub.3
NO.sub.2
155-156
1.20
5-Cl F CF.sub.3
NO.sub.2
1.21
5-Cl Br CF.sub.3
NO.sub.2
1.22
5-Cl CF.sub.3
CF.sub.3
NO.sub.2
1.23
5-Cl OCH.sub.3
CF.sub.3
NO.sub.2
1.24
5-Cl OC.sub.2 H.sub.5
CF.sub.3
NO.sub.2
1.25
5-Cl OC.sub.4 H.sub.9.sup.(n)
CF.sub.3
NO.sub.2
1.26
5-Cl OCF.sub.3
CF.sub.3
NO.sub.2
1.27
5-Cl OCF.sub.2 CHF.sub.2
CF.sub.3
NO.sub.2
1.28
5-Cl OC.sub.6 H.sub.5
CF.sub.3
NO.sub.2
1.29
5-Cl SC.sub.6 H.sub.5
CF.sub.3
NO.sub.2
1.30
5-Cl OC.sub.6 H.sub.4 -p-Cl
CF.sub.3
NO.sub.2
1.31
5-Cl SC.sub.6 H.sub.4 -p-Cl
CF.sub.3
NO.sub.2
1.32
5-Cl H CF.sub.3
NO.sub.2
167-168
1.33
5-Cl H H Cl
1.34
5-Cl H Br NO.sub.2
1.35
5-Cl H Cl NO.sub.2
1.36
5-Cl H CN NO.sub.2
1.37
5-Cl H CONH.sub.2
NO.sub.2
1.38
5-Cl H CON(CH.sub.3).sub.2
NO.sub.2
1.39
5-Cl H COOH NO.sub.2
1.40
5-Cl H COOCH.sub.3
NO.sub.2
1.41
5-Cl Cl CN NO.sub.2
1.42
5-Cl Cl COOC.sub.2 H.sub.5
NO.sub.2
216-220
1.43
5-Cl Cl CONH.sub.2
NO.sub.2
1.44
5-Cl Cl COOH NO.sub.2
1.45
5-Cl H SO.sub.2 CH.sub.3
NO.sub.2
1.46
5-Cl H SO.sub.2 NH.sub.2
NO.sub.2
1.47
5-Cl H SO.sub.2 N(CH.sub.3).sub.2
NO.sub.2
1.48
5-Cl H CH.sub.3
NO.sub.2
1.49
5-Cl H C(CH.sub.3).sub.3
NO.sub.2
1.50
5-Cl H OCF.sub.3
NO.sub.2
1.51
5-Cl H OCF.sub.2 CHF.sub.2
NO.sub.2
1.52
5-Cl H NO.sub.2
CF.sub.3
153-155
1.53
5-Cl H NO.sub.2
Cl 212-213
1.54
5-Cl H NO.sub.2
CH.sub.3
1.55
5-Cl H NO.sub.2
##STR8##
1.56
5-Cl Cl Cl NO.sub.2
1.57
5-Cl Cl Cl Cl
1.58
5-Cl H CF.sub.3
H
1.59
5-Cl Cl H H
1.60
5-CH.sub.3 Cl CF.sub.3
NO.sub.2
1.61
5-CH.sub.3 F CF.sub.3
NO.sub.2
1.62
5-CH.sub.3 H CF.sub.3
NO.sub.2
1.63
5-CH.sub.3 H NO.sub.2
CF.sub.3
1.64
5-CH.sub.3 H NO.sub.2
Cl
1.65
5-CH.sub.3 Cl Cl NO.sub.2
1.66
5-CH.sub.3 Cl CN NO.sub.2
1.67
5-CH.sub.3 Cl COOC.sub.2 H.sub.5
NO.sub.2
1.68
5-Br Cl CF.sub.3
NO.sub.2
136-138
1.69
5-Br Cl CN NO.sub.2
1.70
5-Br Cl COOC.sub.2 H.sub.5
NO.sub.2
1.71
5-Br Cl CONH.sub.2
NO.sub.2
1.72
5-Br F CF.sub.3
NO.sub.2
1.73
5-Br OCH.sub.3
CF.sub.3
NO.sub.2
1.74
5-Br H CF.sub.3
NO.sub.2
1.75
5-Br H CN NO.sub.2
1.76
5-Br H Cl NO.sub.2
1.77
5-Br Cl Cl NO.sub.2
1.78
5-Br H SO.sub.2 CH.sub.3
NO.sub.2
1.79
5-Br H COOCH.sub.3
NO.sub.2
1.80
5-Br H CH.sub.3
NO.sub.2
1.81
5-Br H NO.sub.2
CF.sub.3
154-156
1.82
5-Br H NO.sub.2
Cl
1.83
5-Br H NO.sub.2
##STR9##
1.84
5-Br Cl Cl Cl
1.85
5-CF.sub.3 Cl CF.sub.3
NO.sub.2
1.86
5-CF.sub.3 F CF.sub.3
NO.sub.2
1.87
5-CF.sub.3 H CF.sub.3
NO.sub.2
1.88
5-CF.sub.3 H NO.sub.2
CF.sub.3
1.89
5-CF.sub.3 H NO.sub.2
Cl
1.90
5-CF.sub.3 Cl Cl NO.sub.2
1.91
5-CF.sub.3 Cl CN NO.sub.2
1.92
5-CF.sub. 3 Cl COOC.sub.2 H.sub.5
NO.sub.2
1.93
6-Cl Cl CF.sub.3
NO.sub.2
130-134
1.94
6-Cl F CF.sub.3
NO.sub.2
1.95
6-Cl Br CF.sub.3
NO.sub.2
1.96
6-Cl CF.sub.3
CF.sub.3
NO.sub.2
1.97
6-Cl OCH.sub.3
CF.sub.3
NO.sub.2
1.98
6-Cl OC.sub.2 H.sub.5
CF.sub.3
NO.sub.2
1.99
6-Cl O-n-C.sub.4 H.sub.9
CF.sub.3
NO.sub.2
1.100
6-Cl OCF.sub.3
CF.sub.3
NO.sub.2
1.101
6-Cl OCF.sub.2 CHF.sub.2
CF.sub.3
NO.sub.2
1.102
6-Cl OC.sub.6 H.sub.5
CF.sub.3
NO.sub.2
1.103
6-Cl SC.sub.6 H.sub.5
CF.sub.3
NO.sub.2
1.104
6-Cl OC.sub.6 H.sub.4 -p-Cl
CF.sub.3
NO.sub.2
1.105
6-Cl SC.sub.6 H.sub.4 -p-Cl
CF.sub.3
NO.sub.2
1.106
6-Cl H CF.sub.3
NO.sub.2
1.107
6-Cl H H Cl
1.108
6-Cl H Br NO.sub.2
1.109
6-Cl H Cl NO.sub.2
1.110
6-Cl H CN NO.sub.2
1.111
6-Cl H CONH.sub.2
NO.sub.2
1.112
6-Cl H CON(CH.sub.3).sub.2
NO.sub.2
1.113
6-Cl H COOH NO.sub.2
1.114
6-Cl H COOCH.sub.3
NO.sub.2
1.115
6-Cl Cl CN NO.sub.2
1.116
6-Cl Cl COOC.sub.2 H.sub.5
NO.sub. 2
1.117
6-Cl Cl CONH.sub.2
NO.sub.2
1.118
6-Cl Cl COOH NO.sub.2
1.119
6-Cl H SO.sub.2 CH.sub.3
NO.sub.2
1.120
6-Cl H SO.sub.2 NH.sub.2
NO.sub.2
1.121
6-Cl H SO.sub.2 N(CH.sub.3).sub.2
NO.sub.2
1.122
6-Cl H CH.sub.3
NO.sub.2
1.123
6-Cl H C(CH.sub.3).sub.3
NO.sub.2
1.124
6-Cl H OCF.sub.3
NO.sub.2
1.125
6-Cl H OCF.sub.2 CHF.sub.2
NO.sub.2
1.126
6-Cl H NO.sub.2
CF.sub.3
156-159
1.127
6-Cl H NO.sub.2
Cl
1.128
6-Cl H NO.sub.2
CH.sub.3
1.129
6-Cl H NO.sub.2
##STR10##
1.130
6-Cl Cl Cl NO.sub.2
1.131
6-Cl Cl Cl Cl
1.132
6-Cl H CF.sub.3
H
1.133
6-Br Cl CF.sub.3
NO.sub.2
1.134
6-Br F CF.sub.3
NO.sub.2
1.135
6-Br H CF.sub.3
NO.sub.2
1.136
6-Br H NO.sub.2
CF.sub.3
1.137
6-Br H NO.sub.2
Cl
1.138
6-Br Cl Cl NO.sub.2
1.139
6-Br Cl CN NO.sub.2
1.140
6-Br Cl COOC.sub.2 H.sub.5
NO.sub.2
1.141
6-cyclo-C.sub.3 H.sub.5
Cl CF.sub.3
NO.sub.2
160
1.142
6-cyclo-C.sub. 3 H.sub.5
F CF.sub.3
NO.sub.2
1.143
6-cyclo-C.sub.3 H.sub.5
H CF.sub.3
NO.sub.2
168-171
1.144
6-cyclo-C.sub.3 H.sub.5
H NO.sub.2
CF.sub.3
169-173
1.145
6-cyclo-C.sub.3 H.sub.5
H NO.sub.2
Cl
1.146
6-cyclo-C.sub.3 H.sub.5
Cl Cl NO.sub.2
1.147
6-cyclo-C.sub.3 H.sub.5
Cl CN NO.sub.2
1.148
6-cyclo-C.sub.3 H.sub.5
Cl COOC.sub.2 H.sub.5
NO.sub.2
1.149
6-CH(CH.sub.3).sub.2
Cl CF.sub.3
NO.sub.2
138-141
1.150
6-CH(CH.sub.3).sub.2
F CF.sub.3
NO.sub.2
1.151
6-CH(CH.sub.3).sub.2
H CF.sub.3
NO.sub.2
136
1.152
6-CH(CH.sub.3).sub.2
H NO.sub.2
CF.sub.3
125-131
1.153
6-CH(CH.sub.3).sub.2
H NO.sub.2
Cl
1.154
6-CH(CH.sub.3).sub.2
Cl Cl NO.sub.2
1.155
6-CH(CH.sub.3).sub.2
Cl CN NO.sub.2
1.156
6-CH(CH.sub.3).sub.2
Cl COOC.sub.2 H.sub.5
NO.sub.2
1.157
6-CH.sub.3 Cl CF.sub.3
NO.sub.2
163
1.158
6-CH.sub.3 F CF.sub.3
NO.sub.2
1.159
6-CH.sub.3 H CF.sub.3
NO.sub.2
204-206
1.160
6-CH.sub.3 H NO.sub.2
CF.sub.3
131-132
1.161
6-CH.sub.3 H NO.sub.2
Cl
1.162
6-CH.sub.3 Cl Cl NO.sub.2
1.163
6-CH.sub.3 Cl CN NO.sub.2
1.164
6-CH.sub.3 Cl COOC.sub.2 H.sub.5
NO.sub.2
1.165
6-CN Cl CF.sub.3
NO.sub.2
1.166
6-CN F CF.sub.3
NO.sub.2
1.167
6-CN H CF.sub.3
NO.sub.2
1.168
6-CN H NO.sub.2
CF.sub.3
1.169
6-CN H NO.sub.2
Cl
1.170
6-CN Cl Cl NO.sub.2
1.171
6-CN Cl CN NO.sub.2
1.172
6-CN Cl COOC.sub.2 H.sub.5
NO.sub.2
1.173
6-SC.sub.6 H.sub.5
Cl CF.sub.3
NO.sub.2
1.174
6-SC.sub.6 H.sub.5
F CF.sub.3
NO.sub.2
1.175
6-SC.sub.6 H.sub.5
H CF.sub.3
NO.sub.2
1.176
6-SC.sub.6 H.sub.5
H NO.sub.2
CF.sub.3
1.177
6-SC.sub.6 H.sub.5
H NO.sub.2
Cl
1.178
6-SC.sub.6 H.sub.5
Cl Cl NO.sub.2
1.179
6-SC.sub.6 H.sub.5
Cl CN NO.sub.2
1.180
6-SC.sub.6 H.sub.5
Cl COOC.sub.2 H.sub.5
NO.sub.2
1.181
6-SC.sub.6 H.sub.5
Cl CF.sub.3
NO.sub.2
1.182
6-SC.sub.6 H.sub.5
F CF.sub.3
NO.sub.2
1.183
6-SC.sub.6 H.sub.5
H CF.sub.3
NO.sub.2
1.184
6-SC.sub.6 H.sub.5
H NO.sub.2
CF.sub.3
1.185
6-SC.sub.6 H.sub.5
H NO.sub.2
Cl
1.186
6-SC.sub.6 H.sub.5
Cl Cl NO.sub.2
1.187
6-SC.sub.6 H.sub.5
Cl CN NO.sub.2
1.188
6-SC.sub.6 H.sub.5
Cl COOC.sub.2 H.sub.5
NO.sub.2
1.189
6-OC.sub.2 H.sub.5
Cl CF.sub.3
NO.sub.2
1.190
6-OC.sub.2 H.sub.5
F CF.sub.3
NO.sub.2
1.191
6-OC.sub.2 H.sub.5
H CF.sub.3
NO.sub.2
1.192
6-OC.sub.2 H.sub.5
H NO.sub.2
CF.sub.3
1.193
6-OC.sub.2 H.sub.5
H NO.sub.2
Cl
1.194
6-OC.sub.2 H.sub.5
Cl Cl NO.sub.2
1.195
6-OC.sub.2 H.sub.5
Cl CN NO.sub.2
1.196
6-OC.sub.2 H.sub.5
Cl COOC.sub.2 H.sub.5
NO.sub.2
1.197
4,6-(CH.sub.3).sub.2
Cl CF.sub.3
NO.sub.2
165
1.198
4,6-(CH.sub.3).sub.2
F CF.sub.3
NO.sub.2
1.199
4,6-(CH.sub.3).sub.2
H CF.sub.3
NO.sub.2
215-216
1.200
4,6-(CH.sub.3).sub.2
H NO.sub.2
CF.sub.3
145-152
1.201
4,6-(CH.sub.3).sub.2
H NO.sub.2
Cl
1.202
4,6-(CH.sub.3).sub.2
H C(CH.sub.3).sub.3
NO.sub.2
192-194
1.203
4,6-(CH.sub.3).sub.2
Cl Cl NO.sub.2
1.204
4,6-(CH.sub.3).sub.2
Cl CN NO.sub. 2
1.205
4,6-(CH.sub.3).sub.2
H CN NO.sub.2
203 decomp.
1.206
4,6-(CH.sub.3).sub.2
Cl COOC.sub.2 H.sub.5
NO.sub.2
1.207
4-CH.sub.3, 6-Cl
Cl CF.sub.3
NO.sub.2
148-158
1.208
4-CH.sub.3, 6-Cl
F CF.sub.3
NO.sub.2
1.209
4-CH.sub.3, 6-Cl
H CF.sub.3
NO.sub.2
1.210
4-CH.sub.3, 6-Cl
H NO.sub.2
CF.sub.3
128-133
1.211
4-CH.sub.3, 6-Cl
H NO.sub.2
Cl
1.212
4-CH.sub.3, 6-Cl
Cl Cl NO.sub.2
1.213
4-CH.sub.3, 6-Cl
Cl CN NO.sub.2
1.214
4-CH.sub.3, 6-Cl
Cl COOC.sub.2 H.sub.5
NO.sub.2
1.215
5-CN Cl CF.sub.3
NO.sub.2
1.216
5-CN F CF.sub.3
NO.sub.2
1.217
5-CN H CF.sub.3
NO.sub.2
1.218
5-CN H NO.sub.2
CF.sub.3
1.219
5-CN H NO.sub.2
Cl
1.220
5-CN Cl Cl NO.sub.2
1.221
5-CN Cl CN NO.sub.2
1.222
5-CN Cl COOC.sub.2 H.sub.5
NO.sub.2
1.223
5-CN, 6-CH.sub.3
Cl CF.sub.3
NO.sub.2
>220
1.224
5-CN, 6-CH.sub.3
F CF.sub.3
NO.sub.2
1.225
5-CN, 6-CH.sub.3
H CF.sub.3
NO.sub.2
1.226
5-CN, 6-CH.sub.3
H NO.sub.2
CF.sub.3
125
1.227
5-CN, 6-CH.sub.3
H NO.sub.2
Cl
1.228
5-CN, 6-CH.sub.3
Cl Cl NO.sub.2
1.229
5-CN, 6-CH.sub.3
Cl CN NO.sub.2
1.230
5-CN, 6-CH.sub.3
Cl COOC.sub.2 H.sub.5
NO.sub.2
1.231
4-CH.sub.3, 5-CN, 6-OC.sub.2 H.sub.5
Cl CF.sub.3
NO.sub.2
120
1.232
4-CH.sub.3, 5-CN, 6-OC.sub.2 H.sub.5
F CF.sub.3
NO.sub.2
1.233
4-CH.sub.3, 5-CN, 6-OC.sub.2 H.sub.5
H CF.sub.3
NO.sub.2
1.234
4-CH.sub.3, 5-CN, 6-OC.sub.2 H.sub.5
H NO.sub.2
CF.sub.3
>220
1.235
4-CH.sub.3, 5-CN, 6-OC.sub.2 H.sub.5
H NO.sub.2
Cl
1.236
4-CH.sub.3, 5-CN, 6-OC.sub.2 H.sub.5
Cl Cl NO.sub.2
1.237
4-CH.sub.3, 5-CN, 6-OC.sub.2 H.sub.5
Cl CN NO.sub.2
1.238
4-CH.sub.3, 5-CN, 6-OC.sub.2 H.sub.5
Cl COOC.sub.2 H.sub.5
NO.sub.2
1.239
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
Cl CF.sub.3
NO.sub.2
165-167
1.240
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
Cl CN NO.sub.2
1.241
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
Cl COOC.sub.2 H.sub.5
NO.sub. 2
173-174
1.242
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
Cl CONH.sub.2
NO.sub.2
1.243
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
Cl COOH NO.sub.2
1.244
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
F CF.sub.3
NO.sub.2
1.245
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
OCH.sub.3
CF.sub.3
NO.sub.2
1.246
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
H CF.sub.3
NO.sub.2
1.247
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
H CN NO.sub.2
1.248
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
H Cl NO.sub.2
1.249
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
Cl Cl NO.sub.2
167
1.250
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
H SO.sub.2 CH.sub.3
NO.sub.2
1.251
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
H COOCH.sub.3
NO.sub.2
1.252
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
H CH.sub.3
NO.sub.2
1.253
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
H NO.sub.2
CF.sub.3
183-185
1.254
4-CH(CH.sub.3 ).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
H NO.sub.2
Cl 219-221
1.255
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
H NO.sub.2
##STR11##
1.256
4-CH(CH.sub.3).sub.2, 5-CN, 6-OC.sub.2 H.sub.5
Cl Cl Cl
1.257
5-NO.sub.2 Cl CF.sub.3
NO.sub.2
1.258
5-NO.sub.2 F CF.sub.3
NO.sub.2
1.259
5-NO.sub.2 H CF.sub.3
NO.sub.2
1.260
5-NO.sub.2 H NO.sub.2
CF.sub.3
1.261
5-NO.sub.2 H NO.sub.2
Cl
1.262
5-NO.sub.2 Cl Cl NO.sub.2
1.263
5-NO.sub.2 Cl CN NO.sub.2
1.264
5-NO.sub.2 Cl COOC.sub.2 H.sub.5
NO.sub.2
1.265
6-SO.sub.2 CH.sub.3
Cl CF.sub.3
NO.sub.2
1.266
6-SO.sub.2 CH.sub.3
H NO.sub.2
CF.sub.3
1.267
6-OCH.sub.3 Cl CF.sub.3
NO.sub.2
1.268
6-OCH.sub.3 H NO.sub.2
CF.sub.3
1.269
4-CH.sub.3, 5-CN, 6-OCH.sub.3
Cl CF.sub.3
NO.sub.2
1.270
4-CH.sub.3, 5-CN, 6-OCH.sub.3
H NO.sub.2
CF.sub.3
1.271
4-CH(CH.sub.3).sub.2, 5-CN, 6-OCH.sub.3
Cl CF.sub.3
NO.sub.2
1.272
4-CH(CH.sub.3).sub.2, 5-CN, 6-OCH.sub. 3
H NO.sub.2
CF.sub.3
1.273
4-C.sub.2 H.sub.5, 5-CN, 6-OC.sub.2 H.sub.5
Cl CF.sub.3
NO.sub.2
1.274
4-C.sub.2 H.sub.5, 5-CN, 6-OC.sub.2 H.sub.5
H NO.sub.2
CF.sub.3
1.275
4-CH.sub.3, 6-Br
Cl CF.sub.3
NO.sub.2
1.276
4-CH.sub.3, 6-Br
H NO.sub.2
CF.sub.3
1.277
6-cyclo-C.sub.5 H.sub.9
Cl CF.sub.3
NO.sub.2
1.278
6-cyclo-C.sub.5 H.sub.9
H NO.sub.2
CF.sub.3
1.279
4-cyclo-C.sub.3 H.sub.5, 6-Cl
Cl CF.sub.3
NO.sub.2
1.280
4-cyclo-C.sub.3 H.sub.5, 6-Cl
H NO.sub.2
CF.sub.3
1.281
5-CN, 6-cyclo-C.sub.3 H.sub.5
Cl CF.sub.3
NO.sub.2
1.282
5-CN, 6-cyclo-C.sub.3 H.sub.5
H NO.sub.2
CF.sub.3
1.283
6-OPh-4-Cl Cl CF.sub.3
NO.sub.2
1.284
6-OPh-4-Cl H NO.sub.2
CF.sub.3
1.285
6-OPh-4-CH.sub.3
Cl CF.sub.3
NO.sub.2
1.286
6-OPh-4-CH.sub.3
H NO.sub.2
CF.sub.3
1.287
6-SPh-4-CH.sub.3
Cl CF.sub.3
NO.sub.2
1.288
6-SPh-4-CH.sub.3
H NO.sub.2
CF.sub.3
__________________________________________________________________________
TABLE 2
______________________________________
4-Cyanopyridine derivatives
##STR12##
No. X.sub.m R.sup.1 R.sup.2 R.sup.3 m.p. (.degree.C.)
______________________________________
2.1 6-Cl Cl CF.sub.3
NO.sub.2
2.2 6-Cl Cl CN NO.sub.2
2.3 6-Cl Cl COOC.sub.2 H.sub.5
NO.sub.2
2.4 6-Cl Cl CONH.sub.2
NO.sub.2
2.5 6-Cl Cl COOH NO.sub.2
2.6 6-Cl F CF.sub.3
NO.sub.2
2.7 6-Cl OCH.sub.3
CF.sub.3
NO.sub.2
2.8 6-Cl H CF.sub.3
NO.sub.2
2.9 6-Cl H CN NO.sub.2
2.10 6-Cl H Cl NO.sub.2
2.11 6-Cl Cl Cl NO.sub.2
2.12 6-Cl H SO.sub.2 CH.sub.3
NO.sub.2
2.13 6-Cl H COOCH.sub.3
NO.sub.2
2.14 6-Cl H CH.sub.3
NO.sub.2
2.15 6-Cl H NO.sub.2
CF.sub.3
2.16 6-Cl H NO.sub.2
Cl
2.17 6-Cl H NO.sub.2
##STR13##
2.18 6-Cl Cl Cl Cl
2.19 6-OC.sub.2 H.sub.5
Cl CF.sub.3
NO.sub.2
2.20 6-OC.sub.2 H.sub.5
F CF.sub.3
NO.sub.2
2.21 6-OC.sub.2 H.sub.5
H CF.sub.3
NO.sub.2
2.22 6-OC.sub.2 H.sub.5
H NO.sub.2
CF.sub.3
2.23 6-OC.sub.2 H.sub.5
H NO.sub.2
Cl
2.24 6-OC.sub.2 H.sub.5
Cl Cl NO.sub.2
2.25 6-OC.sub.2 H.sub.5
Cl CN NO.sub.2
2.26 6-OC.sub.2 H.sub.5
Cl COOC.sub.2 H.sub.5
NO.sub.2
2.27 H Cl CF.sub.3
NO.sub.2
2.28 H F CF.sub.3
NO.sub.2
2.29 H H CF.sub.3
NO.sub.2
2.30 H H NO.sub.2
CF.sub.3
2.31 H H NO.sub.2
Cl
2.32 H Cl Cl NO.sub.2
2.33 H Cl CN NO.sub.2
2.34 H Cl COOC.sub.2 H.sub.5
NO.sub.2
2.35 6-OC.sub.6 H.sub.5
Cl CF.sub.3
NO.sub.2
2.36 6-OC.sub.6 H.sub.5
F CF.sub.3
NO.sub.2
2.37 6-OC.sub.6 H.sub.5
H CF.sub.3
NO.sub.2
2.38 6-OC.sub.6 H.sub.5
H NO.sub.2
CF.sub.3
2.39 6-OC.sub.6 H.sub.5
H NO.sub.2
Cl
2.40 6-OC.sub.6 H.sub. 5
Cl Cl NO.sub.2
2.41 6-OC.sub.6 H.sub.5
Cl CN NO.sub.2
2.42 6-OC.sub.6 H.sub.5
Cl COOC.sub.2 H.sub.5
NO.sub.2
2.43 6-Br Cl CF.sub.3
NO.sub.2
2.44 6-Br H NO.sub.2
CF.sub.3
2.45 6-F Cl CF.sub.3
NO.sub.2
2.46 6-F H NO.sub.2
CF.sub.3
2.47 6-SC.sub.6 H.sub.5
Cl CF.sub.3
NO.sub.2
2.48 6-SC.sub.6 H.sub.5
H NO.sub.2
CF.sub.3
2.49 6-SO.sub.2 CH.sub.3
Cl CF.sub.3
NO.sub.2
2.50 6-SO.sub.2 CH.sub.3
H NO.sub.2
CF.sub.3
2.51 6-CN Cl CF.sub.3
NO.sub.2
2.52 6-CN H NO.sub.2
CF.sub.3
______________________________________
TABLE 3
__________________________________________________________________________
5-Cyanopyridine derivatives
##STR14##
No.
X.sub.m R.sup.1
R.sup.2
R.sup.3
m.p. (.degree.C.)
__________________________________________________________________________
3.1
H Cl CF.sub.3
NO.sub.2
159-161
3.2
H Cl CN NO.sub.2
3.3
H Cl COOC.sub.2 H.sub.5
NO.sub.2
3.4
H Cl CONH.sub.2
NO.sub.2
3.5
H Cl COOH NO.sub.2
3.6
H F CF.sub.3
NO.sub.2
3.7
H OCH.sub.3
CF.sub.3
NO.sub.2
3.8
H H CF.sub.3
NO.sub.2
3.9
H H CN NO.sub.2
3.10
H H Cl NO.sub.2
3.11
H Cl Cl NO.sub.2
3.12
H H SO.sub.2 CH.sub.3
NO.sub.2
3.13
H H COOCH.sub.3
NO.sub.2
3.14
H H CH.sub.3
NO.sub.2
3.15
H H NO.sub.2
CF.sub.3
141-144
3.16
H H NO.sub.2
Cl
3.17
H H NO.sub.2
##STR15##
3.18
H Cl Cl Cl
3.19
3-Cl Cl CF.sub.3
NO.sub.2
173-175
3.20
3-Cl F CF.sub.3
NO.sub.2
133-136
3.21
3-Cl Br CF.sub.3
NO.sub.2
3.22
3-Cl CF.sub.3
CF.sub.3
NO.sub.2
3.23
3-Cl OCH.sub.3
CF.sub.3
NO.sub.2
3.24
3-Cl OC.sub.2 H.sub.5
CF.sub.3
NO.sub.2
3.25
3-Cl O-n-C.sub.4 H.sub.9
CF.sub.3
NO.sub.2
3.26
3-Cl OCF.sub.3
CF.sub.3
NO.sub.2
3.27
3-Cl OCF.sub.2 CHF.sub.2
CF.sub.3
NO.sub.2
3.28
3-Cl OC.sub.6 H.sub.5
CF.sub.3
NO.sub.2
3.29
3-Cl SC.sub.6 H.sub.5
CF.sub.3
NO.sub.2
3.30
3-Cl OC.sub.6 H.sub.4 -p-Cl
CF.sub.3
NO.sub.2
3.31
3-Cl SC.sub.6 H.sub.4 -p-Cl
CF.sub.3
NO.sub.2
3.32
3-Cl H CF.sub.3
NO.sub.2
134-135
3.33
3-Cl H H Cl
3.34
3-Cl H Br NO.sub.2
3.35
3-Cl H Cl NO.sub.2
3.36
3-Cl H CN NO.sub.2
210-212
3.37
3-Cl H CONH.sub.2
NO.sub.2
3.38
3-Cl H CON(CH.sub.3).sub.2
NO.sub.2
3.39
3-Cl H COOH NO.sub.2
3.40
3-Cl H COOCH.sub. 3
NO.sub.2
185-187
3.41
3-Cl Cl CN NO.sub.2
3.42
3-Cl Cl COOC.sub.2 H.sub.5
NO.sub.2
182-188
3.43
3-Cl Cl CONH.sub.2
NO.sub.2
3.44
3-Cl Cl COOH NO.sub.2
3.45
3-Cl H SO.sub.2 CH.sub.3
NO.sub.2
>220
3.46
3-Cl H SO.sub.2 NH.sub.2
NO.sub.2
3.47
3-Cl H SO.sub.2 N(CH.sub.3).sub.2
NO.sub.2
3.48
3-Cl H CH.sub.3
NO.sub.2
155
3.49
3-Cl H C(CH.sub.3).sub.3
NO.sub.2
175-178
3.50
3-Cl H OCF.sub.3
NO.sub.2
3.51
3-Cl H OCF.sub.2 CHF.sub.2
NO.sub.2
3.52
3-Cl H NO.sub.2
CF.sub.3
117-119
3.53
3-Cl H NO.sub.2
Cl 135-138
3.54
3-Cl H NO.sub.2
CH.sub.3
3.55
3-Cl H NO.sub.2
##STR16##
134-138
3.56
3-Cl Cl Cl NO.sub.2
3.57
3-Cl Cl Cl Cl 157-158
3.58
3-Cl H CF.sub.3
H 164-170
3.59
3-Cl Cl H H
3.60
3-NO.sub.2
Cl CF.sub.3
NO.sub.2
3.61
3-NO.sub.2
F CF.sub.3
NO.sub.2
3.62
3-NO.sub.2
H CF.sub.3
NO.sub.2
3.63
3-NO.sub.2
H NO.sub.2
CF.sub.3
3.64
3-NO.sub.2
H NO.sub.2
Cl
3.65
3-NO.sub.2
Cl Cl NO.sub.2
3.66
3-NO.sub.2
Cl CN NO.sub.2
3.67
3-NO.sub.2
Cl COOC.sub.2 H.sub.5
NO.sub.2
3.68
3-Br Cl CF.sub.3
NO.sub.2
151-155
3.69
3-Br Cl CN NO.sub.2
3.70
3-Br Cl COOC.sub.2 H.sub.5
NO.sub.2
3.71
3-Br Cl CONH.sub.2
NO.sub.2
3.72
3-Br F CF.sub.3
NO.sub.2
3.73
3-Br OCH.sub.3
CF.sub.3
NO.sub.2
3.74
3-Br H CF.sub.3
NO.sub.2
3.75
3-Br H CN NO.sub.2
3.76
3-Br H Cl NO.sub.2
3.77
3-Br Cl Cl NO.sub.2
3.78
3-Br H SO.sub.2 CH.sub.3
NO.sub.2
3.79
3-Br H COOCH.sub.3
NO.sub.2
3.80
3-Br H CH.sub.3
NO.sub.2
3.81
3-Br H NO.sub.2
CF.sub.3
124-126
3.82
3-Br H NO.sub.2
Cl
3.83
3-Br H NO.sub.2
##STR17##
3.84
3-Br Cl Cl Cl
3.85
3-CF.sub.3
Cl CF.sub.3
NO.sub.2
3.86
3-CF.sub.3
F CF.sub.3
NO.sub.2
3.87
3-CF.sub.3
H CF.sub.3
NO.sub.2
3.88
3-CF.sub.3
H NO.sub.2
CF.sub.3
3.89
3-CF.sub.3
H NO.sub.2
Cl
3.90
3-CF.sub.3
Cl Cl NO.sub.2
3.91
3-CF.sub.3
Cl CN NO.sub.2
3.92
3-CF.sub.3
Cl COOC.sub.2 H.sub.5
NO.sub.2
3.93
4,6-(CH.sub.3).sub.2
Cl CF.sub.3
NO.sub.2
>220
3.94
4,6-(CH.sub.3).sub.2
F CF.sub.3
NO.sub.2
3.95
4,6-(CH.sub.3).sub.2
H CF.sub.3
NO.sub.2
3.96
4,6-(CH.sub.3).sub.2
H NO.sub.2
CF.sub.3
3.97
4,6-(CH.sub.3).sub.2
H NO.sub.2
Cl
3.98
4,6-(CH.sub.3).sub.2
Cl Cl NO.sub.2
3.99
4,6-(CH.sub.3).sub.2
Cl CN NO.sub.2
3.100
4,6-(CH.sub.3).sub.2
Cl COOC.sub.2 H.sub.5
NO.sub.2
3.101
6-Cl Cl CF.sub.3
NO.sub.2
203-204
3.102
6-Cl F CF.sub.3
NO.sub.2
3.103
6-Cl H CF.sub.3
NO.sub.2
3.104
6-Cl H NO.sub.2
CF.sub.3
176-185
3.105
6-Cl H NO.sub.2
Cl
3.106
6-Cl Cl Cl NO.sub.2
3.107
6-Cl Cl CN NO.sub.2
3.108
6-Cl Cl COOC.sub.2 H.sub.5
NO.sub.2
3.109
3,6-Cl.sub.2
Cl CF.sub.3
NO.sub.2
3.110
3,6-Cl.sub.2
F CF.sub.3
NO.sub.2
3.111
3,6-Cl.sub.2
H CF.sub.3
NO.sub.2
3.112
3,6-Cl.sub.2
H NO.sub.2
CF.sub.3
3.113
3,6-Cl.sub.2
H NO.sub.2
Cl
3.114
3,6-Cl.sub.2
Cl Cl NO.sub.2
3.115
3,6-Cl.sub.2
Cl CN NO.sub.2
3.116
3,6-Cl.sub.2
Cl COOC.sub.2 H.sub.5
NO.sub.2
3.117
4-CH.sub.3
Cl CF.sub.3
NO.sub.2
3.118
4-CH.sub.3
H NO.sub.2
CF.sub.3
3.119
6-CH.sub.3
Cl CF.sub.3
NO.sub.2
3.120
6-CH.sub.3
H NO.sub.2
CF.sub.3
3.121
3-Cl, 6-OC.sub.2 H.sub.5
Cl CF.sub.3
NO.sub.2
3.122
3-Cl, 6-OC.sub.2 H.sub.5
H NO.sub.2
CF.sub.3
3.123
3-Cl, 6-OC.sub.6 H.sub.5
Cl CF.sub.3
NO.sub.2
3.124
3-Cl, 6-OC.sub.6 H.sub.5
H NO.sub.2
CF.sub.3
3.125
3-Cl, 6-SO.sub.2 CH.sub.3
Cl CF.sub.3
NO.sub.2
3.126
3-Cl, 6-SO.sub.2 CH.sub.3
H NO.sub.2
CF.sub.3
__________________________________________________________________________
TABLE 4
______________________________________
6-Cyanopyridine derivatives
##STR18##
No. X.sub.m R.sup.1
R.sup.2 R.sup.3
m.p. (.degree.C.)
______________________________________
4.1 H Cl CF.sub.3
NO.sub.2
4.2 H F CF.sub.3
NO.sub.2
4.3 H H CF.sub.3
NO.sub.2
4.4 H H NO.sub.2
CF.sub.3
4.5 H H NO.sub.2
Cl
4.6 H Cl Cl NO.sub.2
4.7 H Cl CN NO.sub.2
4.8 H Cl COOC.sub.2 H.sub.5
NO.sub.2
4.9 3-Cl, 5-CF.sub.3
Cl CF.sub.3
NO.sub.2
4.10 3-Cl, 5-CF.sub.3
F CF.sub.3
NO.sub.2
4.11 3-Cl, 5-CF.sub.3
H CF.sub.3
NO.sub.2
4.12 3-Cl, 5-CF.sub.3
H NO.sub.2
CF.sub.3
4.13 3-Cl, 5-CF.sub.3
H NO.sub.2
Cl
4.14 3-Cl, 5-CF.sub.3
Cl Cl NO.sub.2
4.15 3-Cl, 5-CF.sub.3
Cl CN NO.sub. 2
4.16 3-Cl, 5-CF.sub.3
Cl COOC.sub.2 H.sub.5
NO.sub.2
4.17 3,5-Cl.sub.2
Cl CF.sub.3
NO.sub.2
4.18 3,5-Cl.sub.2
F CF.sub.3
NO.sub.2
4.19 3,5-Cl.sub.2
H CF.sub.3
NO.sub.2
4.20 3,5-Cl.sub.2
H NO.sub.2
CF.sub.3
4.21 3,5-Cl.sub.2
H NO.sub.2
Cl
4.22 3,5-Cl.sub.2
Cl Cl NO.sub.2
4.23 3,5-Cl.sub.2
Cl CN NO.sub.2
4.24 3,5-Cl.sub.2
Cl COOC.sub.2 H.sub.5
NO.sub.2
4.25 3-CF.sub.3 Cl CF.sub.3
NO.sub.2
4.26 3-CF.sub.3 F CF.sub.3
NO.sub.2
4.27 3-CF.sub.3 H CF.sub.3
NO.sub.2
4.28 3-CF.sub.3 H NO.sub.2
CF.sub.3
4.29 3-CF.sub.3 H NO.sub.2
Cl
4.30 3-CF.sub.3 Cl Cl NO.sub.2
4.32 3-CF.sub.3 Cl COOC.sub.2 H.sub.5
NO.sub.2
4.33 5-CF.sub.3 Cl CF.sub.3
NO.sub.2
4.34 5-CF.sub.3 F CF.sub.3
NO.sub.2
4.35 5-CF.sub.3 H CF.sub.3
NO.sub.2
4.36 5-CF.sub.3 H NO.sub.2
CF.sub.3
4.37 5-CF.sub.3 H NO.sub.2
Cl
4.38 5-CF.sub.3 Cl Cl NO.sub.2
4.39 5-CF.sub.3 Cl CN NO.sub.2
4.40 5-CF.sub.3 Cl COOC.sub.2 H.sub.5
NO.sub.2
4.41 4-CF.sub.3 Cl CF.sub.3
NO.sub.2
4.42 4-CF.sub.3 H NO.sub.2
CF.sub.3
4.43 3-NO.sub.2 Cl CF.sub.3
NO.sub.2
4.44 3-NO.sub.2 H NO.sub.2
CF.sub.3
4.45 5-NO.sub.2 Cl CF.sub.3
NO.sub.2
4.46 5-NO.sub.2 H NO.sub.2
CF.sub.3
4.47 5-Cl, 3-CF.sub.3
Cl CF.sub.3
NO.sub.2
4.48 5-Cl, 3-CF.sub.3
H NO.sub.2
CF.sub.3
4.49 6-CN, 3,4,5-Cl.sub.3
Cl CF.sub.3
NO.sub.2
4.50 6-CN, 3,4,5-Cl.sub.3
H NO.sub.2
CF.sub.3
______________________________________
TABLE 5
______________________________________
##STR19##
m.p.
No. X.sub.m /CN
R.sup.1
R.sup.2
R.sup.3
R.sup.4 (.degree.C.)
______________________________________
5.1 3-CN Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
5.2 3-CN Cl CF.sub.3
NO.sub.2
CH.sub.2CHCH.sub.2
5.3 3-CN Cl CF.sub.3
NO.sub.2
CH.sub.2C CH
5.4 3-CN H NO.sub.2
CF.sub.3
COCH.sub.2 Cl
5.5 5-CN Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
5.6 5-CN Cl CF.sub.3
NO.sub.2
CONH.sub.2
5.7 5-CN H NO.sub.2
CF.sub.3
COOCH.sub.2 C.sub.6 H.sub.5
5.8 5-CN H NO.sub.2
CF.sub.3
SO.sub.2 C.sub.6 H.sub.5
5.9 3-Cl, 5-CN H H Cl SO.sub.2 C.sub.6 H.sub.5
5.10 3-Cl, 5-CN Cl CF.sub.3
NO.sub.2
CH.sub.2CHCH.sub.2
5.11 3-Cl, 5-CN Cl CF.sub.3
NO.sub.2
CH.sub.2C CH
5.12 3-Cl, 5-CN H CF.sub.3
H SO.sub.2 C.sub.6 H.sub.5
147-
158
5.13 3-Cl, 5-CN Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
5.14 3-Cl, 5-CN Cl CF.sub.3
NO.sub.2
COCH.sub.3
5.15 3-Cl, 5-CN Cl CF.sub.3
NO.sub.2
COCHCl.sub.2
5.16 3-Cl, 5-CN Cl CF.sub.3
NO.sub.2
COC.sub.6 H.sub.5
5.17 3-Cl, 5-CN Cl CF.sub.3
NO.sub.2
COOCH.sub.3
5.18 3-Cl, 5-CN Cl CF.sub.3
NO.sub.2
CONH.sub.2
5.19 3-Cl, 5-CN Cl CF.sub.3
NO.sub.2
CHO
5.20 3-Cl, 5-CN H NO.sub.2
CF.sub.3
SO.sub.2 C.sub.6 H.sub.5
5.21 3-Cl, 5-CN H NO.sub.2
CF.sub.3
COOCH.sub.3
5.22 3-Cl, 5-CN H NO.sub.2
CF.sub.3
COCH.sub.2 Cl
5.23 6-Cl, 3-CN Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
5.24 6-Cl, 3-CN H NO.sub.2
CF.sub.3
SO.sub.2 C.sub.6 H.sub.5
5.25 6-Cl, 5-CN Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
5.26 6-Cl, 5-CN H NO.sub.2
CF.sub.3
SO.sub.2 C.sub.6 H.sub.5
5.27 4-CH(CH.sub.3).sub.2,
Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
6-OC.sub.2 H.sub.5,
3,5-(CN).sub.2
5.28 4-CH(CH.sub.3).sub.2,
H NO.sub.2
CF.sub.3
SO.sub.2 C.sub.6 H.sub.5
6-OC.sub.2 H.sub.5,
3,5-(CN).sub.2
5.29 5-Cl, 3-CN Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
5.30 5-Cl, 3-CN Cl CF.sub.3
NO.sub.2
COOCH.sub.3
5.31 5-Cl, 3-CN Cl CF.sub.3
NO.sub.2
CONH.sub.2
5.32 5-Cl, 3-CN Cl CF.sub.3
NO.sub.2
COC.sub.6 H.sub.5
5.33 5-Cl, 3-CN H NO.sub.2
CF.sub.3
SO.sub.2 C.sub.6 H.sub.5
5.34 5-Cl, 3-CN H NO.sub.2
CF.sub.3
COOCH.sub.3
5.35 5-Cl, 3-CN H NO.sub.2
CF.sub.3
CONH.sub.2
5.36 5-Cl, 3-CN H NO.sub.2
CF.sub.3
COC.sub.6 H.sub.5
5.37 5-Cl, 3-CN H NO.sub.2
CF.sub.3
COCHCl.sub.2
5.38 6-cyclo-C.sub.3 H.sub.5,
Cl CF.sub.3
NO.sub. 2
SO.sub.2 C.sub.6 H.sub.5
3-CN
5.39 6-CH.sub.3,
Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
3,5-(CN).sub.2
5.40 6-CH.sub.3,
H NO.sub.2
CF.sub.3
SO.sub.2 C.sub.6 H.sub.5
3,5-(CN).sub.2
5.41 6-Cl, 4-CN Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
5.42 6-Cl, 4-CN H NO.sub.2
CF.sub.3
SO.sub.2 C.sub.6 H.sub.5
5.43 4,6-(CH.sub.3).sub.2,
Cl CF.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
3-CN
5.44 4,6-(CH.sub.3).sub.2,
H NO.sub.2
CF.sub.3
SO.sub.2 C.sub.6 H.sub.5
3-CN
5.45 4,6-(CH.sub.3).sub.2,
H CH.sub.3
NO.sub.2
SO.sub.2 C.sub.6 H.sub.5
3-CN
______________________________________
TABLE 6
__________________________________________________________________________
##STR20##
m.p.
No.
X.sub.m /CN R.sup.1
R.sup.2
R.sup.3
M.sup.+ (.degree.C.)
__________________________________________________________________________
6.1
3-CN Cl
CF.sub.3
NO.sub.2
K.sup.+
6.2
3-CN Cl
CF.sub.3
NO.sub.2
N(CH.sub.3).sub.4.sup.+
6.3
3-CN Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.4
3-CN Cl
CF.sub.3
NO.sub.2
C.sub.6 H.sub.5NH(CH.sub.3).sub.2.sup.+
6.5
3-CN Cl
CF.sub.3
NO.sub.2
NH(C.sub.2 H.sub.5).sub.3.sup.+
6.6
3-CN H NO.sub.2
CF.sub.3
K.sup.+
6.7
3-CN H NO.sub.2
CF.sub.3
N(CH.sub.3).sub.4.sup.+
6.8
3-CN H NO.sub.2
CF.sub.3
N(C.sub.4 H.sub.9).sub.4.sup.+
6.9
5-CN Cl
CF.sub.3
NO.sub.2
K.sup.+
6.10
5-CN Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9 .sub.4.sup.+
6.11
5-CN H NO.sub.2
CF.sub.3
N(C.sub.4 H.sub.9).sub.4.sup.+
6.12
3-Cl, 5-CN Cl
CF.sub.3
NO.sub.2
K.sup.+ 175
6.13
3-Cl, 5-CN Cl
CF.sub.3
NO.sub.2
N(CH.sub.3).sub.4.sup.+
198
6.14
3-Cl, 5-CN Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
110-112
6.15
3-Cl, 5-CN Cl
CF.sub.3
NO.sub.2
NH.sub.2 (i-C.sub.3 H.sub.7).sub.2
92-94
6.16
3-Cl, 5-CN Cl
CF.sub.3
NO.sub.2
(CH.sub.3).sub.3 NCH.sub.2 CH.sub.2 OH.sup.+
6.17
3-Cl, 5-CN H NO.sub.2
CF.sub.3
K.sup.+
6.18
3-Cl, 5-CN H NO.sub.2
CF.sub.3
N(C.sub.4 H.sub.9).sub.4.sup.+
6.19
3-Cl, 5-CN H NO.sub.2
CF.sub.3
NH.sub.2 (i-C.sub.3 H.sub.7).sub.2.sup.+
6.20
3-Br, 5-CN Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.21
3-Br, 5-CN H NO.sub.2
CF.sub.3
N(C.sub. 4 H.sub.9).sub.4.sup.+
6.22
5-Cl, 3-CN Cl
CF.sub.3
NO.sub.2
K.sup.+
6.23
5-Cl, 3-CN Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.24
5-Cl, 3-CN H NO.sub.2
CF.sub.3
K.sup.+
6.25
5-Cl, 3-CN H NO.sub.2
CF.sub.3
N(C.sub.4 H.sub.9).sub.4.sup.+
6.26
5-Br, 3-CN Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.27
5-Br, 3-CN H NO.sub.2
CF.sub.3
N(C.sub.4 H.sub.9).sub.4.sup.+
6.28
6-Cl, 3-CN Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.29
6-Cl, 3-CN H NO.sub.2
CF.sub.3
N(C.sub.4 H.sub.9).sub.4.sup.+
6.30
4-CH(CH.sub.3).sub.2, 6-OC.sub.2 H.sub.5,
Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
3,5-(CN).sub.2
6.31
4-CH(CH.sub.3).sub.2, 6-OC.sub.2 H.sub.5,
H NO.sub.2
CF.sub.3
N(C.sub.4 H.sub.9).sub.4.sup.+
3,5-(CN).sub.2
6.32
6-CH.sub.3, 3,5-(CN).sub.2
Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.33
6-CH.sub. 3, 3-CN
Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.34
6-cyclo-C.sub.3 H.sub.5, 3-CN
Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.35
6-Cl, 4-CN Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.36
6-Cl, 4-CN H NO.sub.2
CF.sub.3
N(C.sub.4 H.sub.9).sub.4.sup.+
6.37
4,6-(CH.sub.3).sub.2, 3-CN
Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.38
4,6-(CH.sub.3).sub.2, 3-CN
H NO.sub.2
CF.sub.3
N(C.sub.4 H.sub.9).sub.4.sup.+
6.39
4,6-(CH.sub.3).sub.2, 3-CN
H CH.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
6.40
6-CH(CH.sub.3).sub.2, 3-CN
Cl
CF.sub.3
NO.sub.2
N(C.sub.4 H.sub.9).sub.4.sup.+
__________________________________________________________________________
Generally speaking, the novel compounds are extremely effective on a broad
spectrum of phytopathogenic fungi, in particular those from the
Ascomycetes and Basidiomycetes classes. Some of them have a systemic
action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a large
number of fungi in various crops or their seeds, especially wheat, rye,
barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar
cane, fruit and ornamentals in horticulture and viticulture, and in
vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following
plant diseases:
Erysiphe graminis in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,
Podosphaera leucotricha in apples,
Uncinula necator in vines,
Puccinia species in cereals,
Rhizoctonia species in cotton and lawns,
Ustilago species in cereals and sugar cane,
Venturia inaequalis (scab) in apples,
Helminthosporium species in cereals,
Septoria nodorum in wheat,
Botrytis cinerea (gray mold) in strawberries and grapes,
Cercospora arachidicola in groundnuts,
Pseudocercosporella herpotrichoides in wheat and barley,
Pyricularia oryzae in rice,
Phytophthora infestans in potatoes and tomatoes,
Fusarium and Verticillium species in various plants,
Plasmopara viticola in grapes,
Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the active
ingredients, or treating the seeds of the plants with the active
ingredients. They may be applied before or after infection of the plants
or seeds by the fungi.
The novel substances can be converted into conventional formulations such
as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The application forms depend entirely on the purposes for which they are
intended; they should at all events ensure a fine and uniform distribution
of the active ingredient. The formulations are produced in known manner,
for example by extending the active ingredient with solvents and/or
carriers, with or without the use of emulsifiers and dispersants; if water
is used as solvent, it is also possible to employ other organic solvents
as auxiliary solvents. Suitable auxiliaries for this purpose are solvents
such as aromatics (e.g., xylene), chlorinated aromatics (e.g.,
chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g.,
methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g.,
ethanolamine, dimethylformamide), and water; carriers such as ground
natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground
synthetic minerals (e.g., highly disperse silica and silicates);
emulsifiers such as nonionic and anionic emulsifiers (e.g.,
polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl
sulfonates); and dispersants such as lignin, sulfite waste liquors and
methylcellulose.
The fungicidal agents generally contain from 0.1 to 95, and preferably from
0.5 to 90, wt % of active ingredient. The application rates are from 0.02
to 3 kg or more of active ingredient per hectare, depending on the type of
effect desired. The novel compounds may also be used for protecting
materials, for example against Paecilomyces variotii.
The agents and the ready-to-use formulations prepared from them, such as
solutions, emulsions, suspensions, powders, dusts, pastes and granules,
are applied in conventional manner, for example by spraying, atomizing,
dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 1.239 is mixed with 10 parts by
weight of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is
suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 1.207 is dissolved in a mixture
consisting of 80 parts by weight of xylene, 10 parts by weight of the
adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic
acid-N-monoethanolamide, 5 parts by weight of the calcium salt of
dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40
moles of ethylene oxide and 1 mole of castor oil. By pouring the solution
into water and uniformly distributing it therein, an aqueous dispersion is
obtained.
III. 20 parts by weight of compound no. 3.19 is dissolved in a mixture
consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of
isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide
and 1 mole of castor oil. By pouring the solution into water and finely
distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 1.239 is dissolved in a mixture
consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a
mineral oil fraction having a boiling point between 210.degree. and
280.degree. C., and 10 parts by weight of the adduct of 40 moles of
ethylene oxide and 1 mole of castor oil. By pouring the solution into
water and uniformly distributing it therein, an aqueous dispersion is
obtained.
V. 80 parts by weight of compound no. 1.226 is well mixed with 3 parts by
weight of the sodium salt of diisobutylnaphthalene-.alpha.-sulfonic acid,
10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained
from a sulfite waste liquor, and 7 parts by weight of powdered silica gel,
and triturated in a hammer mill. By uniformly distributing the mixture in
water, a spray liquor is obtained.
VI. 3 parts by weight of compound no. 1.223 is intimately mixed with 97
parts by weight of particulate kaolin. A dust is obtained containing 3% by
weight of the active ingredient.
VII. 30 parts by weight of compound no. 1.234 is intimately mixed with a
mixture consisting of 92 parts by weight of powdered silica gel and 8
parts by weight of paraffin oil which has been sprayed onto the surface of
this silica gel. A formulation of the active ingredient is obtained having
good adherence.
VIII. 40 parts by weight of compound no. 1.200 is intimately mixed with 10
parts by weight of the sodium salt of a phenolsulfonic
acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of
water to give a stable aqueous dispersion. Dilution in water gives an
aqueous dispersion.
IX. 20 parts by weight of compound no. 1.93 is intimately mixed with 2
parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8
parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of
the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and
68 parts by weight of a paraffinic mineral oil. A stable oily dispersion
is obtained.
In these application forms, the agents according to the invention may also
be present together with other active ingredients, for example herbicides,
insecticides, growth regulators, and fungicides, and may furthermore be
mixed and applied together with fertilizers. Admixture with other
fungicides frequently results in an increase in the fungicidal spectrum.
The following list of fungicides with which the compounds according to the
invention may be combined is intended to illustrate, and not restrict, the
combination possibilities.
Examples of fungicides which may be combined with the novel compounds are:
sulfur,
dithiocarbamates and their derivatives, such as
ferric dimethyldithiocarbamate,
zinc dimethyldithiocarbamate,
zinc ethylenebisdithiocarbamate,
manganese ethylenebisdithiocarbamate,
manganese zinc ethylenediaminebisdithiocarbamate,
tetramethylthiuram disulfides,
ammonia complex of zinc N,N'-ethylenebisdithiocarbamate,
ammonia complex of zinc N,N'-propylenebisdithiocarbamate,
zinc N,N'-propylenebisdithiocarbamate and
N,N'-polypropylenebis(thiocarbamyl) disulfide;
nitro derivatives, such as
dinitro(1-methylheptyl)-phenyl crotonate,
2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,
2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and
diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as
2-heptadecylimidazol-2-yl acetate,
2,4-dichloro-6-(o-chloroanilino)-s-triazine,
O,O-diethyl phthalimidophosphonothioate,
5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,
2,3-dicyano-1,4-dithioanthraquinone,
2-thio-1,3-dithio[4,5-b]quinoxaline,
methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate,
2-methoxycarbonylaminobenzimidazole,
2-(fur-2-yl)-benzimidazole,
2-(thiazol-4-yl)benzimidazole,
N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide,
N-trichloromethylthiotetrahydrophthalimide,
N-trichloromethylthiophthalimide,
N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide,
5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,
2-thiocyanatomethylthiobenzothiazole,
1,4-dichloro-2,5-dimethoxybenzene,
4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,
2-thiopyridine 1-oxide,
8-hydroxyquinoline and its copper salt,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide,
2-methylfuran-3-carboxanilide,
2,5-dimethylfuran-3-carboxanilide,
2,4,5-trimethylfuran-3-carboxanilide,
2,5-dimethyl-N-cyclohexylfuran-3-carboxamide,
N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide,
2-methylbenzanilide,
2-iodobenzanilide,
N-formyl-N-morpholine-2,2,2-trichloroethylacetal,
piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide),
1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,
2,6-dimethyl-N-tridecylmorpholine and its salts,
2,6-dimethyl-N-cyclododecylmorpholine and its salts,
N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,
N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine,
1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole
1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triaz
ole,
N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea,
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-one,
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol,
1-(4-phenylphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,
.alpha.-(2-chlorophenyl)-.alpha.-(4-chlorophenyl)-5-pyrimidinemethanol,
5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine,
bis-(p-chlorophenyl)-3-pyridinemethanol,
1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,
1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,
and various fungicides, such as
dodecylguanidine acetate,
3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide,
hexachlorobenzene,
DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate,
methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)-alanate,
N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone,
methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate,
5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,
3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,
3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin,
N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,
2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide,
1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole,
2,4-difluoro-.alpha.-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol,
N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro
-2-aminopyridine, and
1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.
USE EXAMPLES
For comparison purposes,
2-(2,4-dinitro-6-trifluoromethylanilino)-5-trifluoromethylpyridine (A)
disclosed in EP-A 31,257 was used.
USE EXAMPLE 1
Action on Plasmopara viticola
Leaves of potted vines of the Muller-Thurgau variety were sprayed with
aqueous liquors containing (dry basis) 80% of active ingredient and 20% of
emulsifier. To assess the duration of action, the plants were set up,
after the sprayed-on layer had dried, for 8 days in the greenhouse. Then
the leaves were infected with a zoospore suspension of Plasmopara
viticola. The plants were first placed for 48 hours in a water
vapor-saturated chamber at 24.degree. C. and then in a greenhouse for 5
days at from 20.degree. to 30.degree. C. To accelerate and intensify the
sporangiophore discharge, the plants were then again placed in the moist
chamber for 16 hours. The extent of fungus attack was then assessed on the
undersides of the leaves.
The results show that active ingredients 1.197, 1.200, 1.207, 1.223, 1.226,
1.234, 1.239 and 3.19, applied as 0.05 wt % spray liquors, have a better
fungicidal action (95-100%) than prior art comparative active ingredient A
(70%).
USE EXAMPLE 2
Action on Botrytis cinerea in pimientos
Pimiento seedlings of the "Neusiedler Ideal Elite" variety with 4 to 5 well
developed leaves were sprayed to runoff with aqueous suspensions
containing (dry basis) 80% of active ingredient and 20% of emulsifier.
After the sprayed-on layer had dried, the plants were sprayed with a
conidial suspension of the fungus Botrytis cinerea and kept in a
high-humidity chamber at 22.degree. to 24.degree. C. After 5 days, the
disease had spread on the untreated control plants to such an extent that
the necroses covered the major portion of the leaves.
The results show that active ingredients 1.93 and 3.19, applied as 0.05 wt
% spray liquors, have a better fungicidal action (85-95%) than prior art
active ingredient A (0%).
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